Anthraquinone dyestuffs

ABSTRACT

Dyestuffs of the formula   IN WHICH X is an optionally substituted alkylene radical; R is an optionally substituted phenyl radical; and Y is H, Cl, Br or -S-X-OH have been prepared.

United States Patent iiohmmm at a].

[4 1 May 30, 1972 [54] ANTHRAQUINONE DYESTUFF S [72] Inventors: WalterHohmann, Leverkusen; Hans- Samuel Bien, Burscheid, both of Germany [73]Assignee: Farbenfabriken Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: June 20, 1969 [21] App]. No.: 835,222

[30] Foreign Application Priority Data June 29, 1968 Germany". ..P 17 68789.7 June 29, 1968 Germany ..P 17 68 788.6

52 u.s.c| ..260/376, 8/39, 8/40,

260/377, 260/378, 260/379, 260/381 51 mo. ..C09b 11/56 58 Fleldoi'Search..260/378,379,380,376,381

[56] References Cited UNITED STATES PATENTS 2,434,765 1/1948 Grossmann..260/378 Primary Examiner-Lorraine A. Weinberger AssistantExaminerRobert Gerstl Attorney-Plumicy, Tyner & Sandt in which X is anoptionally substituted alkylene radical;

R is an optionally substituted phenyl radical; and Y is H, Cl, Br orS-X--OH have been prepared.

3 Claims, No Drawings ANTHRAQUINONE DYESTUFFS The subject-matter of thepresent invention comprises dyestuffs of the general formula stituted bya hydroxyl group; R and R, stand for optionally substituted alkyl orcycloalkyl radicals; and Y stands for hydrogen, chlorine, bromine orSXOl-l where X has the same meaning as above and the anthraquinonenucleus may contain further substituents, preferably halogen,

and dyestuffs of the general formula in which X stands for an alkyleneradical whichmay be substituted by a hydroxyl group; R and R stand forhydrogen or a substituent; n and m mean the numbers 3; and Y stands forhydrogen, chlorine, bromine or the radical SX-OH where X has the samemeaning as above and the anthraquinone nucleus may contain furthersubstituents, especially chlorine or bromine,

as well as the production and application thereof.

Suitable radicals X are primarily straight-chain or branched alkyleneradicals with one to six carbon atoms, for example, ethylene, propylene,Z-hydroxy-propylene and isobutylene radicalsv Examples of alkyl radicalsR and R, are primarily alkyl radicals with one to eight carbon atoms,which may be substituted, such as methyl, ethyl, n-, iso-propyl, n-,iso-,tert.-butyl, n-, isopentyl, Z-hydroxy-ethyl, 3-methoxypropyl,benzyl, phenyl-a or -,6-ethyl, l phenyl--methyl-hexylene-( 3hexahydrobenzyl, y-dimethyl-amino-propylenamino, fl-aminoethyl,'y-arninopropyl, B-acetaminoethyl radicals.

The cycloalkyl radicals are preferably cyclohexyl radicals which maycontain one or more of the substituents'customary in anthraquinonechemistry, such as optionally substituted alkyl radicals, preferablythose with one to four carbon atoms. for example, methyl, ethyl, n-,iso-propyl, n-, iso-or tert.-butyl radicals; optionally alkylatedhydroxyl or amino groups, such as the hydroxyl, methoxy, amino, oracetylamino group.

The radicals R and R, or R and R may be identical or different.

Suitable substituents R and R are those customary in anthraquinonechemistry, such as alkyl radicals, preferably lower alkyl radicals withone to six carbon atoms, such as methyl, ethyl, n isoand tert.-butyl,n-, iso-pentyl, hydroxyethyl radicals; alkoxy radicals, preferablyalkoxy radicals with one to four carbon atoms, which may be substituted,such as methoxy, ethoxy, propoxy, 2-hydroxyethoxy, 3-hydroxypropoxy,2-methoxy-ethoxy radicals; alkylmercapto radicals, preferably those withone to four carbon atoms such as methylmercapto, ethylmercapto-radicals;halogen atoms such as fluorine, chlorine or bromine; amino groups whichmay in turn be substituted by alkyl, acyl or cycloalkyl radicals such asamino, methylamino, dimethylamino, cyclohexylarnino, acetylamino,propionylamino, butyrylamino, acetylmethylamino, ,Q-hydroxyethylamino,B-hydroxyacetylamino, ,B-methoxyacetylamino groups; hydroxyl groups.

Suitable dyestuffs (ll) are, for example, those of the formula zlu Y, 0NHQ Y2 (l i fi i l in which Y, and Y stand for hydrogen, chlorine,bromine or SX--OH but cannot simultaneously denote hydrogen, chlorine orbromine, 1 as well as those of the formula i R 2)n my f) in which Y, andY as well as R R n and m have the same meaning as above.

' Examples of dyestuffs (1) according to the invention are theanthraquinones mentioned in the following, which are substituted in the6- or 7-position, or in the 6,7-position by B- hydroxyethyl-thio,,B'ydihydroxypropyl-thio, 'y-hydroxypropyl-thio,a-methyl-y-hydroxypropyl-thio groups, or in the 6(7)-position by one ofthe aforesaid hydroxyalkyl thio groups and in the 7(6)-position bychlorine or bromine: l,4-dicyclohexylamino-, l,4-di-o-, m-,p-methyl-cyclohexyl-amino-, 1,4-di-ethyl-cyclohexylamino-, l,4-di-n-,iso-propyl-cyclohexylamino, l,4-di-p-tert.-butyl-cyclohexylamino,l,4-di-o-, m-, p-hydroxy-cyclohexylamina, I,4-di-m-,p-amino-cyclohexylamino-, l,4-di-m-, p-acetamin0-cyclohexylarnino-,lcyclohexylamino-4-o-, m-, p-methyl-cyclohexylamin0-,lcyclohexylamino-4-o-, m-, p-hydroxy-cyclohexylamino-,lcyclohexylamino-4-m-, p-arnino, or -acetamino-cyclohexylamino-, 1-o-,m-, p-methyl-cyclohexylamino-4-m-, p-hydroxy- ,-aminoor'-acetarninocyclohexylamino-,l-cyclohexylamino-4-hexahydro-benzylamino-, l-cyclohexylamino-4-benzylamino-, l-cyclohexaylamino-4-phenyl-aor -/3- ethylamino-,l-cyclo-hexylamino-4-nor -iso-propylamino l- 0-, m-,p-methyl-cyclohexylarnino-4-nor -iso-propylarnino-,l,4-di-methyl-amino-, 1,4-di-n-, iso-p ropylaminm, l-n'(iso)-propylamino-4-iso(n)-propylamino-, l ,4-di-benzylarnino-,I,4-di-hexahydro-benzylamino-, l,4-di-a or B-phenylethylamino-,l,4-di-n-, iso-, tert.-butylamino-, l,4-di-[1-phenyl-S-methyl-hexylen-amino( 3 l ,4-di-B-hydroxyethylarnino-,l,Ldifi-methoxy-ethylarnino-, l,4-di-B-ethoxyethylamino-,1,4-di-y-dimethyl-arnino-propylenamino-, 1,4- di-fl-arnino-ethylarnino-,l,4-di-B-acetamino-ethylamino-,lisopropylamino-4-B-hydroxy-ethyl-amino-anthraquinone.

Examples of dyestuffs (ll) according to the invention are anthraquinoneswhich are substituted in the 5-01 6position or in the 5,8- or6,7-position by B-hydroxy-etl'iyl-thio, 3,7- dihydroxypropyl-thio,'y-hydroxypropyl-thio, a-methyl-'yhydroxypropyl-thio groups, or in the5(8) or 6(7)-position by a B-hydroxyethyl-thio, B,'y-hydroxypropyl-thio, -y-hydroxypropyl-thio,a-methyl-y-hydroxypropyl-thio group and in the 8(5)- or 7(6) -positionby chlorine or bromine, such as l,4-di- 0-, m-, p-anisidino-; l,4-di-o-,m-, p-toluidino-; l,4-di-anilin0-; l,4di-o-, m-, p-chloro-anilino-;l,4-di-o-, m-, p-bromoanilino-; l,4di-m, p-fluoro-anilino-; l,4-di-o-,m-, pphenetidino-; l,4-di-o-, m-, p-hydroxy-anilino-; l,4-di-m-,phydroxyethoxy-anilino-; l,4-di-o-, m-, p-amino-anilino-; l,4- di-o, m-,p-acetaminoanilind; l,4-di-o-, m-, p-hydroxyacetamino-anilino-;l,4-di-m, p-hydroxyethyl-amino-anilino-; l,4-di-m-, p-[n-, is0-,tert.]-butyl-anilino-; l,4-di-m-, p-carbomethoxy-anilino-;l,4-di-carbethoxy-anilino-; ll,4-di-m-, pmethylthio-anilinol,4-di-[2,3-; 2,4-; 2,5-; 2,6-; 3.4-; 3,5-dimethyl anilino-;l,4-di-[2,4,6-; 2,3,4-; 2,4,5,-tri-methyl]- anilino-; l ,4di-[2,6-di-ethyl-4-methyl ]-anilino-; l Adi-13- methyl-4-hydroxy or 4-methyl-3-hydroxy]-anilino-; l,4-di-]3- (4 )-methyl-4-( 3 )-methoxy]anilino-; 1,4-di-l 3-chloro4- methyl or -methoxy]-anilino-;1,4-di-[3-methyl or chloro-4- acetamino1-anilinoql,4-di-p-cyclohexyl-anilino-; l-anilino-4- m-, p-anisidino-;l-anisidino-4-o-, m-, p-anisidino-; l-o-, mp-anisidino-4-o-, m-,p-toluidino-; l-anilino-4-o-, m-, ptoluidino-; l-anilino-4-o-, m-,p-acetamino-anilino-; 1-0-, m-, p-toluindino-4-o-, m-,p-acetaminoanilino-; l-o-, m-, panisidino-4-o-, m-, p-acetamino-anilino;lanilino-4-o-, m-, phydroxy-anilino-; l-[2,3-; 2,4-; 2,5-; 2,6-; 3,4-;3,5-dimethyl]- anilino-4-o-, m-, p-toluidino or -anisidino-', l-o-, m-,ptoluidino-4-[p-acetamino-phenyl l-anilinoanthraq uinone.

If two radicals I-IOXS are present, these may be identical or different.

Dyestuffs of the general formula (I) can be obtained from compounds ofthe general formula 0 I\|IH--R l l Z2- in which Z, and 2 stand forhydrogen, chlorine or bromine, but cannot Simultaneously denotehydrogen, by the exchange of one or two halogen atoms for the radicalSXOH with thiols HSX'OI-I. If Z and A stand for halogen, one or twohalogen atoms may be exchanged. In the case where different mercaptansare used, final dyestuffs with different thioether groups -SXOH canbeobtained by the exchange of two halogen atoms.

Suitable thinls are, for example O-II CH The halogen exchange ispreferably carried out in an organic solvent, for example, in methanol,ethanol, butanol, isopropanol, N-methyl-pyrrolidone, e-caprolactam,pyridine, chlorobenzenes, glycol ethers, but preferably in dimethylformamide. The reaction can be carried out at room temperature as wellas at an elevated temperature, for example, at temperatures of 200 C,preferably at 60 130 C. It may take place in the presence ofacid-binding agents, for example, in the presence of alkali metalcarbonates, alkali metal alcoholates, alkali metal hydroxides, and/ortertiary amines, for example, triethylamine, triethanolamine orN-methyl-N,N- diethanolamine.

The products obtained by the exchange of halogen may be subsequentlyhalogenated, for example, with chlorine or bromine or with the usualhalogenating agents.

The compounds of the general formula (V) can be obtained either by theexchange of the a-positioned halogen atoms in compounds of the generalformula (VI) or by the exchange of the hydroxyl groups in compounds ofthe general formula r r 1? F H QA z Zzi H I Y H 0 X 4) OH (Vl) (VII) inwhich 2, and Z, have the same meaning as above, and X, and X stand forchlorine or bromine, for optionally substituted alkylorcycloalkyl-am'ino radicals of the type mentioned above and, if desired,by subsequent oxidation of the leuco reaction products primarily formedfrom (VII).

in compounds of the formula (VI) or (VII), only one of the a-positionedsubstituents may initially be exchanged for an alkylor cycloalkyl-aminoradical. When the intermediate products so prepared, which still containa chlorine or bromine atom or a hydroxyl group in the 4-position areisolated and reacted in a second reaction step with another alkylorcycloalkyl-amine, then there are obtained anthraquinones which aresubstituted in the 1,4-position by different alkyland/orcycloalkyl-amino radicals.

Compounds which are essentially the same but usually contain more orless substantial proportions of the corresponding symmetrical1,4-dialkylor cycloalkyl-amino-anthraquinone derivatives, can also beobtained in one reaction step, i.e. without isolation of themonoreaction products, either by using the alkylor cycloalkyl-amine tobe initially reacted only in a slight excess over the amount of aminetheoretically required for the monosubstitution, optionally in thepresence of a solvent, for example, nitrobenzene, the second reactioncomponent being added and reacted only after the conversion is completeand, if necessary, at elevated temperatures, or by immediately reactingwith a mixture of two alkyland/or cycloalkylamines.

The reactions are generally carried out at an elevated temperature, forexample, at 200 C. when starting from (VI), at 50 C when starting from(VII), and optionally in the presence of an acid-binding agent, such asan alkali metal carbonate or acetate.

The reactions are preferably carried out in organic solvents, forexample, in methanol, ethanol, isopropanol, butanol, isobutanol, glycolmonomethyl ether, or in an excess of the reacting alkylorcycloalkylamines, or in mixtures of these solvents with water,preferably in the presence of boric acid when starting from (VII), andin butanol, glycol or diglycol ethers, dimethyl formamide,chlorobenzenes, nitrobenzene of in an excess of the reacted amines whenstarting from (VI).

The compounds (VII) can be prepared from the corresponding quinizarinesby reduction according to processes known from the literature. Suitablereducing agents are for example, sodium dithionite, zincdust/hydrochloric acid, aluminum powder/sulphuric acid, ironlglacialacetic acid, or the leuco compound of the anthraquinone derivativesused.

A variant of the process described above consists in that initially thesubstituents Z and/or 2 in compounds of the formu la exchanged for theradicals I-IO-X--S; the reaction product of the formula 3 R H OX- S I (lOH (IX) in which Y, stands for hydrogen, halogen or is then reduced toform the corresponding leuco compound; the hydroxyl groups are thensimultaneously or successively exchanged for identical or differentalkyiand/or cyclo-alkyl amino radicals; and, if desired, the leucoreaction products are oxidized by methods known from the literature toform the corresponding anthraquinone derivatives. in general, however,this procedure offers no advantage over the processes described above.

The dyestuffs of the formula (ll) can be obtained from compounds of thegeneral formula 5 in which Z stands for chlorine or bromine; p for thenumbers l or 2; and R R n and m have the same meaning as above, byexchanging the substituent Z for the radical S- X-OH by the reactionwith thiols HS-X-OH, one or two substituents being exchangeable, andoptionally by subsequent chlorination or bromination. The use ofdifferent thiols leads to final dyestuffs with different radicals S-XOH.

The exchange of Z for S-XOH is preferably carried out in an organicsolvent, for example in methanol, ethanol, butanol, isopropanol,N-methyl-pyrrolidone, e-caprolactam, pyridine, chlorobenzene,o-dichlorobenzene of glycol monomethyl ether, but preferably in dimethylformamide. The reaction can be carried out at room temperature as wellas at an elevated temperature, for example, at temperatures in the rangefrom 20to 200 C, preferably 60 130 C. It may take place in the presenceof acid-binding agents, for example, in the presence of alkali metalcarbonates, alkali metal alcoholates, alkali metal hydroxides, and/ortertiary amines, for example, triethylamine, triethylamine orN-methyl-N,N- diethanolamine.

The resultant products may be subsequently halogenated, for example,with chlorine or bromine or with the usual halogen-yielding agents.

The compounds of the formula (X) in which the substituent orsubstituents Z stand in the B-position, can be obtained by the exchangeof the a-positioned halogen atoms in compounds of the general formula 14(Xgll in which R R n and m have the same meaning as above. It ispossible initially to exchange only one of the a-positioned halogenatoms for an arylamine radical. When the intermediate product soprepared, which still contains a halogen atom in the a-position, isisolated and reacted in a second operation with another arylamine' thenthere are obtained diarylamino-anthraquinone derivatives which carrydifferent substituents in the 1,4-position.

Compounds which are essentially the same but usually contain smallproportions of the corresponding diarylamino derivatives which aresymmetrical in the 1,4-position, can also be obtained in one reaction,i.e. without isolation of the monosubstitution product, by either usingthe arylamine initially to be reacted only in a slight excess over theamount theoretically required, optionally in the presence of a solventsuch as nitrobenzene, and adding and reacting the second reactioncomponent only when this has been converted and, if desired, at elevatedtemperatures, or by immediately reacting with a mixture of twoarylamines.

The reactions are generally carried out at an elevated temperature, forexample, at 220 C, and generally in the presence of an acid-bindingagent, such as an alkali metal carbonate or acetate, optionally with theaddition of catalytic amounts of copper or its salts. Suitable solventsa re, for example, butanol, glycol and diglycol ethers, dimethylformamide, chlorobenzenes, nitrobenzene or, preferably, an excess of thereacting amines.

Compounds of the formula (X) in which the substituent or substituents Zstand in the aor }3- position, can be obtained by the exchange of the OHgroups in compounds of the general formula g (XIX) in which 2' and phave the same meaning as above, for arylamines of the formulae (Xll) and(Xlll). lt is possible either first to prepare (XIV) by methods knownform the literature, optionally isolating this compound and reacting itwith arylamines, or to carry out the preparation of (XIV) from thecorresponding quinizarines and the reaction with arylamines in a singlereaction step. Here, too, it is possible to react simultaneously orsuccessively with identical or different arylamines.

Suitable reducing agents for the preparation of the leuco compounds are,for example, sodium dithionite, zinc dust/hydrochloric acid,aluminum/sulphuric acid, iron/acetic acid, or the leuco compound of theanthraquinone derivative used.

The reaction is preferably carried out in organic solvents, for example,in methanol, ethanol, isopropanol, butanol, isobutanol, glycolmonomethyl ether or in an excess of the reacting arylamine, or inmixtures of these solvents with water, preferably in the presence ofboric acid, The reaction proceeds already at room temperature and ispreferably carried out at an elevated temperature, for example, at 60 C.

.A variant of the process described above consists in exchanging thesubstituent or substituents Z in compounds of the formula XV in which Zand p have the same meaning as above, for the radical S.XOH, andsubsequently exchanging the hydroxyl groups for arylamine radicals,possibly after etherification of the hydroxyl groups or reduction of thereaction product to form the leuco compound. In general, however, thisprocedure offers not advantages.

The new dyestuffs are finely divided in the usual way, for example, bypasting with sulphuric acid or an organic solvent. They are suitable fordyeing and printing synthetic fiber materials, especially those ofsynthetic polyamides, for example, those of poly-e-caprolactam or ofcondensation products from hexamethylenediamine and adipic acid. Thegreenish blue to blue dyeings obtained are generally characterized bygreat clarity and good general fastness properties, particularly by goodfastness to light and washing.

The parts givenin Examples are parts by weight, unless otherwise stated;the temperatures are degrees Centigrade.

EXAMPLE 1 a. 100 parts l,4-dicyclohexylamino-6-chloro-anthraquinone aresuspended in 100 parts dimethyl formamide at 1 15 120 and mixed with 30minutes with a solution of 25,2 parts thioglycol and 18.4 partspotassium hydroxide in 25.2 parts methanol. The reaction mixture isstirred at l 10 for 20 minutes, poured onto 1,000 parts of ice water,some concentrated hydrochloric acid is added to improve the filteringproperty, the product is filtered off with suction, washed neutral, anddried. 109 Parts1,4-di-cyclohexyla.mino-dhydroxyethylmercapto-anthraquninone of goodquality are obtained.

Since under the reaction conditions the solubility of 1,4-dicyclohexylamino--chloro-anthraquninone in dimethyl formamide islimited, whereas that of the reaction product is not, it is advantageousto react the 1,4-di-cyclohexyl-amino-6- chloro-anthraquinone with thethioglycol in portions. With this method the reaction mixture remainsreadily stirrable throughout the whole of the reaction time.

b. The l,4-di-cyclohexylamino-6-chloro-anthraquinone used in (a) can beobtained as follows, for example:

100 Parts l,4,6-trichloro-anthraquinone (obtained by chlorination ofanthraquinone-B-sulphonic acid in oleum according to German Pat. No.216,071 and subsequent treatment with nascent chlorine according toGerman Pat. No. 214,714) and 500 parts cyclohexylarnine are boiled underrefluxfor 5% hours. The reaction mixture is diluted with 500 partsethanol, the product'which is precipitated in the form of blue needlesis filtered off with suction while hot, washed with hot ethanol untilthe drainage liquid is clear blue, and finally thoroughly with hotwater. After drying, there are obtained 89.5 parts.

EXAMPLE 2 If the 1,4-di-cyclohexylamino-6-chloro-anthraqunione isreplaced in Example 1(a) with an equal stoichiometric amount ofl,4-di-cyclohexylamino6-bromoanthraquinone (obtainable in analogy withExample 1(b) from 1,4-dichlorofi-bromo-anthraquinone or1,4,6-tribromo-anthraquinone), then the same reaction and working upalso yields 1,4-dicyclohexylamino-6-hydroxymethylmercapto-anthraquinoneof good quality in an almost theoretical yield.

EXAMPLE 3 a. 50 parts l,4-di-n-propylamino-6,7-dichloro-anthraquinoneare dissolved in 250 parts dimethyl formamide and mixed within 10minutes at 100 105 with a solution of 13 parts thioglycol and 9.4 partspotassium hydroxide in 13 parts by volume of methanol, and the reactionmixture is further stirred at the same temperature for l0 minutes. Themixture is diluted with 500 parts methanol, stirred for several hourswhile cooling with ice, the product is filtered off with suction anssuccessively washed with methanol and water. 41 parts I,4-di-n-propylamine-6-hydroxyethylmercapto-7-chloroanthraquinone areobtained.

b. The l,4-di-n-propylamino-6,7-dichloro-anthraquinone use in (a) can beobtained as follows:

100 Parts leuco-6,7-dichloro-quinizarine (obtainable, for example, bytreating 6,7-dichloro-quinizarine with aluminum powder in concentratedsulphuric acid at 50 55), 300 parts n-propylamine, 1,000 parts by volumeof ethanol and a solution of 10 parts of boric acid in 50 parts of waterare boiled under reflux and with access of air for 5 hours. The reactionproduct which is precipitated when the mixture is stirred cold, iffiltered off with suction when cold, washed with ethanol and water, anddried. 72 Parts are obtained.

EXAMPLE 4 a. 70 Parts I ,4-di-cyclohexylamino-6,7-dichloroanthraquinoneare stirred in 300 parts dimethyl formamide and mixed at I l0 within 20minutes with a solution of 16.5 parts thioglycol and 12 parts potassiumhydroxide in 16.5 parts methanol. Stirring is continued at the sametemperature for 30 minutes. The reaction mixture is diluted with 300parts by volume of methanol, stirred cold, the precipitated reactionproduct is filtered off with suction in the cold, was methanol and hotwater. After drying, there are obtained 59 parts 1,4-di-cyclo-hexylamino-o-hydroxyethylmercapto-7-chloroanthraquinone. Thisproduct contains about 10 percent each ofl,4-di-cyclohexyl-amino-6,7-clichloro-anthraquinone and 1,4-di-cyclohexyl-amino-6,7-dihydroxyethylmercaptoanthraquinone.

b. 29 Parts of the. product obtained according to (a) are dissolved in120 parts dimethyl formamide and mixed at 100 l05 within l0 minutes witha solution of 7.3 parts thioglycerol and 3.8 parts potassium hydroxidein 7.3 parts methanol. Stirring is continued at for 30 minutes, themixture is diluted with l20 parts methanol, stirred cold, the reactionproduct which is precipitated in the form of small needles is filteredofi" with suction and washed with methanol and cold water. 23 Partsl,4-di-cyclohexylamino-6-hydroxyethylmercapto-7B,'y-dihydroxy-propylmercapto-anthraquinoneare obtained.

c. If the potassium salt of thioglycerol is replaced in (b) with anequal stoichiometric amount of the potassium salt of thioglycol, thenthe same procedure yieldsl,4-di-cyclohexylamino-6,7-di-hydroxyethylmercapto-anthraquinone.

The same product can also be obtained by a simpler method according tothe following single step process:

99 Parts l,4-di-cyclohexylamino-6,7-dichloro-anthraquinone are stirredat 100 1 10 into 500 parts dimethyl formamide, and the suspension ismixed within 20 minutes with a solution of 35 parts thioglycol and 25.5parts potassium hydroxide in 35 parts methanol. The mixture is diluteswith 200 parts methanol, stirred cold, the product is filtered off withsuction and successively washed with methanol and hot water. 94 Partsare obtained after drying.

d. A product similar to that of (b) is obtained when 47 parts1,4-di-cyclohexylamino-6,7-dichloro-anthraquinone in l70 parts dimethylformamide are mixed at 100 with a solution of 9.75 parts thioglycol,13.5 parts thio-glycerol and 14 parts potassium hydroxide in 25 partsmethanol, the mixture is diluted with parts methanol and worked up asdescribed under (b). The product contains higher proportions ofl,4-di-cyclohexylamino-6,7-di-hydroxyethylmercaptoand l,4-di-cyclohexylamino-6,7-di-B;y-dihydroxypropylmercaptoanthraquinone asimpurities than the reaction product obtained according to (b).

e. The l,4di-cyclohexylamino-6,7-dichloro-anthraquinone used in theExamples 4(a) (d) can be obtained as follows:

100 Parts I,4,6,7-tetrachloroanthraquinone are boiled under reflux with500 parts cyclohexylarnine for 1% hours, and the mixture is diluted with250 parts by volume of ethanol. The precipitated product is filtered offwith suction while warm, washed with hot ethanol, boiled with dilutehydrochloric acid, washed until neutral, and dried. 72 Parts of pureproduct are obtained.

EXAMPLE 5 a. 10 Parts l,4-di-cyclohexylamino--chloro-anthraquinone aredissolved in 50 parts dimethyl formamide and the solution oi oi 05 05 mI A v 3 m io io io m m 5 .5 5 io mo io w 25m 5 5 58m 5 E0 1 50$ 50 l 50m I 12 6 m mo mo mo m m 6 .oflzmm HHQLWHULHHO'WI mo mo mmo w I I I I I II I 1 I I I v :OU I 1 I v I I I I |OU|..|. -O -O .IOU I I I 1 I I I I lI I I I I I I p I l I .5 6 mo mo mo m 65 2 6 6 :miam nmo mo 50 Eu 6:3 II l I fiuafio m mo mo fio m m 6 Q g Q E mo mo mo m mo mo mo 6 6 3 Q 6 QQEO EQ? aw Bim 6 6 38m 25w 4. 5 mo I No m I mo H .558 m mo mv mo m m 6 a25m w Cw a im 6w c m SHEEN m H H 548 5 3v 0 5 5 w .h. m .5 w 5 W M M 5 m6 7 7 e e mmwmmm mmmm. x n a v. c n n z 1. e u 0 w d b 8M .m R R I u d 8:m e e f 0 e h 0 f m l v c H H m em a a c N N mm ml m m o; 10 B mum mm 5d e mwwmmwmmn mm dcme Lm w mmm m Y Y m V..C w b I. y e m mm 36 P m m dmmm 7 mmmwnmimmmwmam m f mmwm flcam i I n I U m n n m m m ww o .mN 1Nommm mm a mmmmwhmm m m0 hmm ad xym 6 n d u m 1 .g mm m wm A m P o r f 1e r m. e fi e x o n. e o m v. 7. Km u m e m m. d 7 .m o m m e o M P P re w m P t last column refer to poly The reaction products B of Table I]can be obtained by the method described in Example 5 from the startingcompounds A by reaction with thioglycerol. The shades given in the lastcolumn refer to polyamide dyeings obtained according to the dyeinginstruction of Example 66.

.5 E m fiomofio m 3 k E mo 6Q m -mUm -m w daaw 8m 6 6 1.52m 165mm h lowam am am am W Mm m m V Hm .I v i r i Z. 5 j mv m mo mmomO mo m MM 70 awHMO 62m 6 mo mumw mo m 38m 25m 6 6 w 505mm 3 4 mo AMV mo A m v mo A w vmo mv 5 5 3 0 m mo momu mnu m r m -O mw we no E mofiomw mo w mo mommfmom 5 1.05% 6 6 w 5 5% i m 3 6 6 mofiomo mo m l 6 6 55 Cw PW 3 PW w 3m 3m0355M v a m NJQ F 5 w m x m m M w w m w H EXAMPLE 65 synthetic polyamidein a 10 Parts by weight of a fabric of bath containing 400 parts ofwater, 0.2 parts 1,4-di-cyclohex- -'a.nthraquinone (obtained dividedform and 0.2 parts ylamino-o-hydroxyethylmercapto according toExample 1) in finely of a conventional dispersing agent are slowlyheated to boiling temperature and dyed at the boil for 1 hour. Thematerial is subsequently rinsed, Slightly soaped, if desired, and dried.A

very clear greenish blue dyein g of very good fastness to washing, lightand rubbing is obtained.

EXAMPLE 66 A printing paste is prepared from 10 parts1,4-di-npropylamino 6-hydroxyethylmercapto-7-chloro anthraquinone(obtained according to Example 2) in finely divided form, parts GlyecinA thiodiethylene glycol, 50 parts urea, 500 parts of a 12 percent carobbean flour ether thickening, and made up with water to 1,000 parts.

2 This printing paste is applied to a fabric of synthetic polyamideaccording to known processes by machine or screen printing, the fabricis dried, steamed in a Mather-Flatt a P paratus at 102 for 10 minutes,subsequently rinsed in the usual way andsoaped. A clear blue print ofvery good fastness 30 to washing, light and rubbing is obtained.

I EXAMPLE 67 If the1,4-di-cyclohexylamino-fi-hydroXyethyLmercaptoanthraquinone in Example65 or the l,4-di-n. propyl-amino-6- hydroxyethylmercapto-anthraquinonein Example 66 replaced with equal parts of the products obtainableaccording to Examples 3 5, then clear blue prints or dyeings arelikewise obtained.

In the same way the dyestufis of Examples 6-64 yield dyeings and printsof the shades indicated in the last column of- Tables I and 11.

EXAMPLE 68 a. 452 Parts l,4-di-m-toluidino-6-chloro-anthraquinone aresuspended at 100 in 452 parts dimethyl formamide. This suspension isadmixed at 1001 10 within 20 minutes, while stirring, with a solution of102 parts thiogl I toluidino-6 quality,

Since under the reaction conditions the solubility of1,4-dim-toluidino-o-chloroanth limited, whereas that of raquinone indimethyl-fonnamide is the reaction product is not, it is recommended toreact the material in portions in order that the mixture remainsstirrable.

b. The l,4-di-m-toluidino-6-ch1oro-anthraquinone used in (a) is obtainedas follows: 311.5 Parts 1,4,64richloro-anthraquinone (crude product,obtained by chlorination of anthraquinone fi-sulphonic acid according toGerman Pat. No. 216,071 and subsequent treatng to German Pat. No.

ment with nascent chlorine accordi 214,714) are heated with 1,250 partsm-toluidme and 138 parts sodium carbonate at for 12 hours, while stirmomO mom 6 mo momo mo m m mosmomO mo m MEOAEO MHO a mOSWO mO mmmu EOQmO mOmO mO mOm mO NO EO mO mO mO mww A w i umoil muo mo mo 2.25 use;

EXAMPLE 69 a. 487 Parts l,4-di-m-toluidino-5,8-dichloro-anthraquinoneare stirred at 100 120 into 487 partsdimethyl formamide. To thesuspension which is readily stirrable there is added at 120' 110 within15 minutes a solution of 97.5 parts of thioglycol and 70 parts potassiumhydroxide in 97.5 parts methanol, and stirring is continued at 1 forminutes.

The mixture is diluted with 480 parts by volume of methanol, stirring iscontinued for 2 hours while cooling with ice, the product is filteredoff with suction and the filtered material is successively washed with1,000 parts by volume methanol and hot water. After drying, there areobtained 440 parts1,4-di-m-toluidino-5-hydroxyethyl-mercapto-8-ch1oroanthraquinone. Thisproduct contains about 10 percent each of 1,4-di-m-toluidino-5,8-dihydroxyethyl-mercaptoanthraquinone and1,4-di-m-toluidino-5,8-dich1oroanthraquinone as impurities.

The l,4-di-m-toluidino-5,8-dichloro-anthraquinone used above can beobtained according to one of the following instructions:

b; 200 Parts leuco-5,8-dichloro-quinizarine [obtained from crude5,8-dichloro-quinizarine (German published specification No. 1,199,279,Example7)], 600 parts m-toluidine and 2,000 parts by volume ethanol aremixed with a solution of parts boric acid in 60 parts of water and themixture is boiled under reflux for 6 hours, for the last 4 hours withaccess of air. The reaction product which is precipitated in the form ofblue needles is filtered ofi with suction while hot, washed withhotethanol until the blue-green drainage liquid is clear, and finally withhot water. 155.5 Parts are obtained.

0. 225 Parts 5,8-dich1oro-quinizarine (obtained according to Germanpublished specification No. 1,199,279; Example 7) are dissolved in 1,100parts by volume of m-toluidine at 85, 22.5 parts boric acid, 260 partsby volume of concentrated hydrochloric acid and 39 parts of zinc dustare added, and the mixture is stirred at 100 for 2% hours. The mixtureis stirred cold, the product is filtered off with suction, the filteredmaterial is washed with 200 parts m-toluindine and methanol and finallyboiled with dilute hydrochloric acid; 175 Parts are obtained.

d. If the 5,8-dichloro-quinizarine is replaced in (c) with a mixture of165 parts 5,8-dichloro-quinizarine and 60 partsleuco-5,8-dichloro-quinizarine, and only 200 parts by volume ofconcentrated hydrochloric acid and 30 parts zinc dust are added, thenthe same reaction and working up yields 213 pans.

EXAMPLE 70 a. 12.9 Parts I,4-di-anilino-5,8-dibromo-anthraquinone aredissolved in 50 parts dimethyl formamide and the solution is mixed at 90100 with 4.65 parts thioglycol (in the form of a concentrated ethanolicsolution potassium salt.) Stirring is continued at 100 105 for minutes,the mixture is cooled to 10, the precipitated dyestuff is filtered offwith suction, washed with a little dimethyl formamide, subsequently withhot water, and dried. 8.2 Parts l,4-di-anilino-5,8-dihydroxyethylmercapto-anthraquinone are obtained.

b. The 1,4-di-anilino-5 ,B-dibrQmo-anthraquinone can easily be obtainedfrom 5,8-dibromoquinizarine by one of the methods described under 69 (b)(d).

EXAMPLE 71 a. 6.3 Parts 1,4-di-p-anisidino 5-chloro-anthraquinone aredissolved in parts dimethyl formamide and the solution is mixed with2.05 parts thioglycol (on the form of a concentrated solution of thepotassium salt in dimethyl formamide) at and stirred at the sametemperature for 20 minutes. 15 parts of'water are then added dropwise,the product is filtered off with suction and washed with water.After-drying, there are obtained 5.05 parts l,4-di p-anisidino-5-hydroxyethylmercapto-anthraquinone.

b. The l,4-di-p-anisidino-5-chloro-anthraquinone used in (a) can beobtained as follows:

84 Parts leuco-S-chloro-quinizarine (obtained from 5-clfloro-quinizarine by reduction with aluminum in concentrated sulphuricacid at 55) are boiled under reflux with 250 p-anisidine, 850 parts byvolume of ethanol, and 9 parts boric acid (dissolved in 60 parts ofwater) for '1 1 hours; stirring is continued for 12 hours withoutheating, the product is filtered off with suction, and washed withethanol and water. 109 Parts -l,4-di-p-anisidino-S-chloro-anthraquinoneare obtained, which still contains a small amount of the leucocondensation product. The leuco component can easily be oxidized bybrief boiling with nitrobenzene or by prolonged heated with pryidine,possibly. with the addition of a few drops of piperidine.

EXAMPLE 72 8.5 Parts 1,4-di-m-toluidino-6,7-dichloro-anthraquinone aredissolved in 40 parts dimethyl formamide, 3.6 parts thioglycol in theform of methanolic solution of thepotassium salt are added dropwise at100 105 in the course of 20 minutes, and stirring is continued at thesame temperature for 20 minutes. The mixture is diluted with 70 partsmethanol, the product is filtered off with suction, washed with methanoland hot water. 7.4 Partsl,4-di-m-toluidino-6,7-dihydroxyethylmercapto-anthraquinone areobtained.

b. The 1,4-di-m-toluidino-6,7-dichloro-anthraquinone can be obtained inthe following way, for example:

8.5 Parts l,4,6,7-tetrachloro-anthraquinone (obtainable e.g. bychlorination of 2,3-dichloro-anthraquinone in oleum) are stirred in 42.5pans m-toluidine with the addition of 5 parts sodium acetate at 180 185for 5 hours. After cooling to 80, the mixture is diluted with 45 partsethanol, the precipitated product is filtered 01f with suction nearboiling temperature, and washed with hot ethanol and water. 9.4 Parts1,4-di-m-toluidino-6,7-dichloro-anthraquinone are obtained.

EXAMPLE 73 on an ice bath, the product is filtered off with suction andthe filtered material washed with methanol and water.

There are obtained 7.4 parts of a mixture of 1-o-anisidino-4-p-toluidino-6-hydroxyethylmercapto-anthraquinone andl-oanisidino-4-p-toluindino-7-hydroxy-ethylmercaptoanthraquinone.

It, instead of the product obtained according to (b), mixtures obtainedaccording to (c), (d), or (e) are used in (a) in the same way, then thesame procedure yields products which are somewhat less pure but have thesame valuable dyeing properties.

i The mixtures used in (a) are obtained as follows:

b. 31.1 Parts of technical 1,4,6-trichloro-anthraquinone, 21.3 partssodium acetate and parts by volume of panisidine are heated withchromatographic control at until approximately equal amounts of startingmaterial and di-chloro exchange product are present, besides the 88 ee am svmo fio mo w l m 810 O E O .qofimeqm m A8 mo mo mo m Q g 6 AS mo momo m 2. 6 8V 6 3: t Q 56 avmo mo wo m w 25 3 {seam 595 E g flo mo mo m Oand seats; e 5 e aotaetmoxwl H. H. HuHHH HHHM HHHH Hu 55 ea s 4e .EEM32; S mo mo io w so mo io mo w 58...: E5 1.2.3.-. fi saw E 6 so mo io mom ....oe..:. E 6 ....-..oe.. g state? Maggi- -NW w ew d9: a .I x l denims w ww m A8 mo mo mo m .5223 mm w dbon m H A8 -O 055: me 05am e n 05cmmo o mom mo flow Q A V 6 Q Q e sw Cw m "M W cw 8H m e um m a a moose 5 51 2 u w n x w m n v. 3 y m a 5 m m m n m n m m m w m m Dim ..m m n l a za a m a t m o w n J J G s S .1 M a m a m m m H 2 H m t t e 0 N -N .d W mm e w .I M m m D. g OH O B 0 d V t r m m i i S d m. 1

anthraquinone.

Parts p-toluidine are then added, the mixture is EXAMPLE 746-dihydroxyethylmercapto-anthraquinone.

mono-chloro exchange product (about 30 minutes are required). Themixture is diluted with parts ethanol stirred cold until the precipitateno longer increases, the latter is filtered off with suction, washedwith ethanol and water. There are obtained 23.4 parts of a mixture ofl-o-anisidino- 5 4,6- and -4,7-dichloro- 20 parts of this mixture areheated with 14 parts sodium acetate and 100 parts p-toluidine at 180 185for 8 hours while stirring. The mixture is diluted with 100 partsdiethylene 1Q glycol monomethyl ether, the product is filtered ofi withsuction when cold, washed with diethylene glycol monometh ether andwater. 20. 1 Parts are obtained.

Mixtures which are similar but contaminated with the symmetricalchlorine exchange products l,4-di-oanisidine-6- chloroanthraquinoneanthraquinone can be obtained by the methods described under (c)(e).

c. 31.1 Parts l,4,6-trichloro-anthraquinone are reacted with 20 90 partsby volume of o-anisidine at as described in (b), by the reaction isalready interrupted when chromatographic control indicates that thestarting material and 1,4-dio-anisidine-6-chloro-anthraquinone arepresent in. a ratio of 2:1. heated at until only small amounts ofmonoarylamino reaction products can be detected described under b).

d. 31.1 Parts l,4,6-trichloro-anthraquinone is stirred with a 30 mixtureof 100 parts o-anisidine and 50 25 parts p-toluidine with the additionof 20 parts sodium acetate at 180 for 12 hours and worked up asdescribed under (b).

e. 85 Parts leuco-fi-quinizarine are boiled under reflux for 15 hourswith 250 parts of a mixture of otoluidine in a ratio of 2 and a solutionof 9 parts boric acid in 60 parts of water, air having access for thelast 10 hours. The mixture is stirred cold the precipitated reactionproduct is filtered ofi' with sucti and successively washed with ethanoland water.

a. 10 Parts l,4-di-m-toluidino--chloro-anthraquinone are dissolved in 40parts dimethyl formamide, and the solution is 50 mixed within 30 minutesat 105 with a warm solution of 3.8 parts thioglycerol and 2.0 partspotassium hydroxide in 5 ethanol. The mixture is diluted with 75 partsethanol is continued for several hours with cooling, the product isfiltered off with suction, washed with ethanol and water.

After drying, there are obtained 7.8 toluidino- The reaction products Bof Table 1 can be obtained by one 60 of methods described in Examples68(11) 73(a) fro starting materials a of Table 1 by reaction with thifigures in brackets refer to the substitution anthraquinone nucleus. Theshades given in refer to polyamide dyeings obtained accordin tion ofExample 131.

mm mo mw mo 6 as 6 mo mo io m 6v 6 2v 6 6 mo mo I mo 1 .5 m 6 mo mo mo mO Q As 6 v Q 4 O 2: g i i Y i 5w 5% iw mm. 6 m 6 mo mo mo m m 6 6 .596 mv mo io iu m 3v mo mo mo m S 38m 25 3 38m A6 6 A2 6 62 m 3 25m 92 8 25 ii 5 i m 6 mo mo mo m m 5 6 -3 6.56 6 mo io mo m m 6 6 3 m6 0 E6 56 o 5 6c Q My .5. E moLmoLmolml 6 moLmoLmolml Q 6 6 6 6 0 Q 2 56 o 56 o "66% E60 m Q Q m 6 Q Q X Y Q- 6 mo io io m m 6 6 2 6 6 6 6 .35 5596 As mo mo mow Q Q m 6 6 Q 666 as 6 As mo mo mo w 8- 8 6 6 As 6 586.35 3v mo mo io mw 256 w @v 6 25 EQ Q $6 I mo A V mo l Q m 3v mo mO mo m m 8v 6 .l 6 E 66V mo mo mo m 5 5w 5 6 6 25 mo mo m mm Fl m w .526 535 av mo mo mo m OQ6 6 5 PW Gr m m C .N g "M SQEQKH m 31 The reaction products B of 'lable2 can be obtained by the method described in Example 5 from the startingcompounds A by reaction with thioglycerol. The figures in brackets referim :2:o :c- 50 Q Q 6 a: :2 II: III Ill :5 h :5 i=5 :,7 50 8:0 1. Q :Q gEDO Q Ill! 0 zoiola io m :cic :c io w :ocQt 26 E6 527g! so :a $6:csfiirw io m .....-s... E5 210 2 r l i &2 EV :c g 6 :oio zw io m m.5255 so 5 Q 6 1515686 :5: 5.5 27 :oio o io w i As 6 l 5 5 a w i E m2552. s m w m x w w 6 6 m to the substitution positions in theanthraquinone molecule. The shades given in the last column refer topolyamide dyeings obtained according to the instruction of Example 13 I.

O NH-Rz Shade Green.

c1 6 Co Example EXAMPLE 131 a. 10 Parts by weight of a fabric ofsynthetic polyamide in a bath containing 400 parts of water 0.2 parts1,4-di-mto]uidino-6-hydroxyethylmercapto-anthraquinone (obtainedaccording to Example I) in finely divided form and 0.2 parts of aconventional dispersing agent, are slowly heated to boiling temperatureand dyed at the boil for 1 hour. The material is subsequently rinsed,slightly soaped, if desired, and dried. A 10 deep green dyeing of verygood fastness to washing, light and rubbing is obtained.

EXAMPLE 132 A printing paste is prepared from 10 partsl,4-di-mtoluidino6-hydroxyethylmercapto-anthraquinone (in finely dividedform), 30 parts Glyecin A thiodiethylene glycol, 50 parts urea, 500parts of a 12 percent carob bean flour ether thickening, and made up to1,000 parts with water.

2 This paste is applied to a fabric of synthetic polyamide according toknown processes by machine orscreen printing, the fabric is dried andsteamed in a Mather-Flatt apparatus at 102 for 10 minutes, andsubsequently rinsed and soaped in the usual way. A green print of verygood fastness to washing, light and rubbing is obtained.

EXAMPLE 133 If the l,4-di-m-toluidino-6-hydroxyethylmercaptoanthraquinone is replaced inExample 131 or 132 with the same amounts of dyestufi's obtained inExamples 69 74, then the dyestuff of Example 69(a) yields yellowishgreen, that of 70(a) yields bluish-green, those of 71 74(0) yield greendye- 3 5 ings or prints of good to very good fastness properties.

If the l ,4-di-m-to]uidino-6-hydroxyethylmercaptoanthraquinone isreplaced in Examples 131 or 132 with the same amounts of the dyestuffsof the Tables I and 2, then dyeings or prints are obtained in the shadesgiven in the last in which R and R, are selected from the groupconsisting of hydrogen, alkyl of one to six carbon atoms, hydroxyalkylwith one to six carbon atoms, alkoxy with one to four carbon atoms,hydroxyalkoxy with one to four carbon atoms, methoxyalkoxy with one tofour carbon atoms in the alkyl radical, alkyl mercapto with one to fourcarbon atoms, fluoro, chloro, bromo, amino, methylamino, dimethylamino,cyclo-hexylamino, acetylamino, propionylamino, butyrylamino,acetylmethylamino, hydroxy-ethylamino, hydroxyacetylamino,methoxy-acetylamino, and hydroxy; chloroacetyl-amino,

methylacetylamino, cyclohexyl, acetarninophenyl, carbomethoxy andcarbo-ethoxy;

X is an alkylene radical or an alkylene radical substituted on OHwherein alkylene means a member selected from the group C straight-chainalkylene and C branched chain alkylene;

Y is H, Cl, Br, or a radical SX-OH; wherein the anthraquinone nucleusmay contain further Cl or Br substituents wherein ii and m stand foranumber from 0-3.

2. Dyestuffs claim 1 of the formula in which Y and Y stand for hydrogen,chlorine, bromine of -SXchlorine or bromine.

in which Y, and Y stand for hydrogen, chlorine, bromine or SX-OH butcannot simultaneously denote hydrogen, chlorine or bromine. 1 5 l '0 8I! UNITED STATES PA'IER'F OFFICE CERTIFICATE 0F CORRECTION latent No.3,666,778 Dated Ma 30, 1972 Inventor) Walter Hohmann et al It iscertified that error appears in the above -identified patent and thatsaid Letters Patent are hereby corrected as shown below:

I Column 5, line 37, "triethylamine" should read ---triethanol amine---.

Colunm 6, line 29, "form" should read --from--.

Column 6, line 46, the comma should be a period.

Column 7, line 7, "25,2" should read ---25.2--. v

Column 7, line 14, "anthraquininone" should read' -anthraquinone.

Column 7, line 16, ."anthraquninone" should read --anthraquinone--.

Column 8, line 6, "was" should read ---washed with Column 9, line 3 "a"should read -acid-.

Column 12, Example 28 Table I, "S-CH CH IOH" should read 2 2 ---SCH CH-'0H--- s 2 2 Column 13, Example 34, Table I, 3

Q I C -CH should read C-CH 3 I I t .7 in all four 1 instances.

FORM O-1050 (IO-69)

2. Dyestuffs claim 1 of the formula
 3. Dyestuffs of claim 1 of theformula